Terpene isomerization in liquid phase



Patented Sept. 11, 1945 assess: rmrmm sosmmzsrion m mourn muss Robert w. Martin, Savannah. Ga., asslgnor to Hercules Powder Company, Wilmington, Del, a corporation of Delaware No Drawing. Application Fehruary 19, 1948, Serial No. 415,48!

20 Claims- (CL 280 6'l5.5)

This invention relates to improvements in terpene isomerizatron, and more particularly relates to the isomerizatlon of bicyclic terpenes to a mixture oi monocyclic, bicyclic, and acyclic terpenes particularly rich in dipentene, allo-ocimene, and camphene and specifically to the liquid phase isomerization of terpenes in the presence of water.

Many methods have been reported in the literature for th isomerization oi terpenes using various conditions of heating and various types of catalysts. Most methods show that catalysts having an acidic reaction are necessary to the isomerization process. However, when an acid type catalyst is used poor yields of terpene isomers are obtained because of the excessive side reaction in the form of polymerization. when heat alone is used, such high temperatures are required to eiiect a reaction that the products of pyrolytic decomposition predominate. The use of an alkaline type catalyst permits a greater degree of selective isomerization and a greater yield of isomer because of the decreased amount of polymerization.

Now, in accordance with the present invention, it has been discovered that a bicyclic terpene may be isomeriaed to a desirable mixture of monocyclic, bicyclic, and acyclic terpene isomers rich in dipentene with a minimum amount of polymer by heating the terpene in the presence oi water at a temperature above the boiling point of the terpene and while maintaining the mixture in a liquid phase.

A method of carrying out the process or this invention is illustrated by the following specific examples, which are not to be construed as limiting, and in which the parts expressed are by Exams-ll One partofgumturpentine andonepartof water were charged into a steel vessel equipped with means for agitating the mixture and tar maintaining a pressure. The vessel was heated to 270 C. and held at this temperature for onehalf hour. The mixture was constantly agitated duringthe heatingperlod. Thevesselwasthen cooled'and the contents removed. The ofl layer had a refractive index m of 1.4880. The density or the layer was 0.8604 at 15.6 C. Analysis of the layer indicated the presence of monocyclic terpenes particularly rich in dipentene.

distilled water and commercial alpha-pinene (95% alpha-pinene) were charted into an autoclave and heat applied. when the temperature reached 180" 0., the mixture was agitated and kept agitated for a period of two hours during which time the temperature was maintained at 227 C. $2.5 C. Samples were withdrawn at intervals The progress of the isomerization was followed by noting the change of the specific rotation oi the mixture. Dlll'illl the two hours of the pinene present when the temperature reached 227 C. was isomeriaed. The mixture was cooled and allowed to separate into an oil layer and a water layer. 91% of the oil layer was steam volatile. The steam-volatile portion had a reiractive index (n of 1.4153 and a specific rotation (1 of +lL45. Analysis of the oil layer indicated the presence of a mixture of monocyclic terpene monomers particularly rich in dipentene.

The iollowing examples were carried 0% in substantially the same way described with reference to the above examples with changes in condition Equal partsoi weisht: of operation as shown in the iollowins table:

Table Physical characteristic 0 a 4, of humor reoo Ex. Terpcne Parts x 2 Parts time Remarks c a r:

C 3-... Commercial issue 1 H 0-- 0f 09 h mggmpmge). I 1 250=h25 21111-.-- 1 4190 +3.78 73: m mm i l 4...- do 1 carried out in l M- 8'0 1 Q0 mins. LBB 0.8532 Wig, mu d mltllbllll- Percent Fraction No. of still charge Total mu.

One oi the unexpected results obtained when using water in accordance with the present inventioncontrastedtotheuseoi anacld,isthe appearance of allo-ocimene in the products of isomerisatlon. Also. when isomerisation is carried out in the presence of water. about -l2% oi camphene appears in the product. This high or camphene is entirely unexpected since it has never been found in the product obtained by the spontaneous or by the acid catalytic isomerisation oi alpha-pinene in either the liquid or vapor phases. Spontaneous isomerization concerns isomerization without the assistanoe oi a catalyst.

Bicyclic terpenes and particularly alpha-pinene may be isomer-iced to a desirable mixture of monocyclic, bicyclic, and acyclic terpenes particularly rich in dipentene, by heating in liquid phase above the boiling point of the terpene and in the presence of water.

The terpenes capable of being isomerized under the conditions or this invention are the bicyclic terpenes as, for example, alpha-pinene and beta pinene. Bicyclic terpene-containing materials as, for example, the oleoresins obtainable from the pine tree, and the more volatile components 0! the oleoredns as. for example, the material known as turpentine may be used. Gum and wood turpentine are particularly desirable for purposes of isomerization to monocyclic terpenes rich in dipentene because of the presence of a large amount oi alpha-pinene.

Operable conditions of heating in accordance with the present invention are those temperatures which are above the boiling point of the terpene being lsomerized and below its critical temperature. Under normal conditions of operation, the upper temperature limit will be about 300 C. It is preferred to carry out the heating within a. temperature range between about 225 C. and about 275 C. and a substantially optimum condition of temperature is 250 0.1-2.5 C.

The catalytic agent operable in accordance with this invention is water. The proportion of terpene to water may be varied within wide limits. It is preferred to use from about 10 parts of terpene to about 1 part of water to about equal parts of terpene and water.

The isomerisation of the terpenes is carried out while maintaining the terpene component and the water component oi the mixture of terpene and water in the liquid phase or in a liquid condition by the suitable means of pressure. Pressures as high as 1200 to 1400 pounds per square inch may be used when heating the terpene at 275 C. in order to keep the system in the liquid phase. Intimate contact between the components of the mixture may be obtained by any suitable means as, for example, a stirring mechanism or agitator. It is desirable to maintain the mixture under constant agitation during the heating operation.

The process may be carried out continuously by passing the mixture of alpha-pinene or other terpenes capable of being isomerized under the conditions of this invention together with water through suitable tubes or other chambers maintained at a temperature above the boiling point 01' the terpene being isomerized and at a pressure suiiicient to maintain the components of the mixture in a liquid state.

In accordance with the process of the present invention bicyclic terpenes may be isomerized by heating the terpene at a temperature above its boiling point in the presence or water while maintaining the components of the system in a liquid condition. The monocyciic terpene isomers resulting from the heat treatment in the presence of water may be selectively hydrogenated to carvo-menthene in substantially quantitative yields at pressures of from 1 to 3 atmospheres and temperatures below about C.

What I claim and desire to protect by Letters Patent is:

l. The process or isomerizing a bicyclic terpene containing material which comprises heating the material above its boiling in liquid phase in the presence of eiiective amounts of water as the sole catalyst.

2. The process of isomeriaing a bicyclic terpene containing material which comprises heating said material at a temperature between about its boiling point and about 300' C. in liquid phase in the presence oi eflective amounts or water as the sole catalyst.

3. The process of isomerizing a bicyclic terpene containing material which comprises heating said material at a temperature between about 225 C. and about 275 C. in liquid phase in the presence 01' effective amounts 01' water as the sole catalyst.

4. The process 01' iscmerizlng a bicyclic terpene-containing material which comprises heating said material at a temperature between about 225 C. and about 275 C. in liquid phase in the presence oi water as the sole catalyst in an amount by weight ranging from about 1 to about 0.1 times the amount by weight of said material.

5. The process 01' isomerizing a bicyclic terpene which comprises heating the terpene above its boiling point in liquid phase in the presence 01' eflective amounts or water as the sole catalyst.

6. The process ofisomerizing a pinene which comprises heating the pinene above its boiling point in liquid phase in the presence of eii'ective amounts of water as the sole catalyst.

I. The process of isomerizing turpentine which comprises heating the turpentine above its boiling point in liquid phase in the presence oi eflective amounts or water as the sole catalyst.

8. The process of isomerizing alpha-pinene which comprises heating the pinene above its boiling point in liquid phase in the presence of eflective amounts oi water as the sole catalyst.

9. The process 01' isomerlzing beta-pinene which comprises heating the pinene above its boiling point in liquid phase in the presence of eflective amounts of water as the sole catalyst.

10. The process or isomerizing turpentine which comprises heating the turpentine at a temperature between about its boiling point and about amounts oi water as the sole catalyst.

11. The process of isomer-fining aipha-pinene liquid phase in the presence oi effective amounts which comprises heating the pinene at a temperaf W t a t S019 (BB-$517819.

ture between about its boiling point and about The Process of lsvmerizins -P 8 300 c. in liquid phase in the presence of effective which comprises heating t e n ne at a temperamounts of water as the S018 Catalyst 5 ature of about 250 C. in liquid phase in the pres- The process f isomeflzmg bampinene ence of effective amounts or water as the sole which comprises heating the pinene at a tempercatalyst- 18. The process of isomerizing turpentine which comprises heating the turpentine at a temperature of between about 225 C. and about 275 C, in liquid phase in the presence of water as the sole catalyst in an amount by weight ranging from 1 gsg g iz iz mi gg fi fi g zzf 'ffg g i about 1 to about 0.1 times the amount by weight of turpentine.

liquid phase in the presence of efiectii e amounts {5 The process of isomeflzmg alphmpmme of water as the sole catalyst which comprises heating the pinene at a temper The Pmcess mmerizmg alpha'pmene ature between about 225 c. and about 2'15" 0. in 222 fz g gg g g g 3:53?- iiquid phase in the presence of water as the sole 9 ween a catalyst in an amount by weight ranging from liquid phase in the presence of effective amounts 20 about 1 to about 01 times the amount by weight ature between about its boiling point and about 300 C. in liquid phase in the presence of effective amounts of water as the sole catalyst.

13. The process of isomerizing turpentine which of water as'the sole catalyst. of pinene 15. The process of isomerizing alpha-pinene 20, The process of isomerizing beta-pinene which comprises heating the pinene at a temperawhich comprises heating the pinene at a tempertu e of bout 50 C- in liquid Phase in the presature between about 225 C. and about 275 C. in time efiective amounts of Water as the $018 25 liquid phase in the presence of water as the sole catalyst. catalyst in an amount by weight ranging from 16. The process of isomerizing beta-pinene about 1 to about 0.1 times the amount by weight which comprises heating the pinene at a temperof terpene.

ature between about 225 C. and about 275 C. in ROBERT W. MARTIN.

CERTIFICATE OF CORRECTION.

Patent No. 2,58l l 82. 1 September 11, 191

ROBERT w. MARTIN.

It is hereby certified that error appears in the printed specification of therabove numbered patent requiring correction as follows: Page 2, second column, line 28, claim 1, after "boiling" insert --point--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 11th day of December, A. D. 1915.

Leslie Frazer (Seal) First Assistant Commissioner of Patents.

11. The process of isomer-fining aipha-pinene liquid phase in the presence oi effective amounts which comprises heating the pinene at a temperaf W t a t S019 (BB-$517819.

ture between about its boiling point and about The Process of lsvmerizins -P 8 300 c. in liquid phase in the presence of effective which comprises heating t e n ne at a temperamounts of water as the S018 Catalyst 5 ature of about 250 C. in liquid phase in the pres- The process f isomeflzmg bampinene ence of effective amounts or water as the sole which comprises heating the pinene at a tempercatalyst- 18. The process of isomerizing turpentine which comprises heating the turpentine at a temperature of between about 225 C. and about 275 C, in liquid phase in the presence of water as the sole catalyst in an amount by weight ranging from 1 gsg g iz iz mi gg fi fi g zzf 'ffg g i about 1 to about 0.1 times the amount by weight of turpentine.

liquid phase in the presence of efiectii e amounts {5 The process of isomeflzmg alphmpmme of water as the sole catalyst which comprises heating the pinene at a temper The Pmcess mmerizmg alpha'pmene ature between about 225 c. and about 2'15" 0. in 222 fz g gg g g g 3:53?- iiquid phase in the presence of water as the sole 9 ween a catalyst in an amount by weight ranging from liquid phase in the presence of effective amounts 20 about 1 to about 01 times the amount by weight ature between about its boiling point and about 300 C. in liquid phase in the presence of effective amounts of water as the sole catalyst.

13. The process of isomerizing turpentine which of water as'the sole catalyst. of pinene 15. The process of isomerizing alpha-pinene 20, The process of isomerizing beta-pinene which comprises heating the pinene at a temperawhich comprises heating the pinene at a tempertu e of bout 50 C- in liquid Phase in the presature between about 225 C. and about 275 C. in time efiective amounts of Water as the $018 25 liquid phase in the presence of water as the sole catalyst. catalyst in an amount by weight ranging from 16. The process of isomerizing beta-pinene about 1 to about 0.1 times the amount by weight which comprises heating the pinene at a temperof terpene.

ature between about 225 C. and about 275 C. in ROBERT W. MARTIN.

CERTIFICATE OF CORRECTION.

Patent No. 2,58l l 82. 1 September 11, 191

ROBERT w. MARTIN.

It is hereby certified that error appears in the printed specification of therabove numbered patent requiring correction as follows: Page 2, second column, line 28, claim 1, after "boiling" insert --point--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 11th day of December, A. D. 1915.

Leslie Frazer (Seal) First Assistant Commissioner of Patents. 

